Halocarbon hydrogenolysis

ABSTRACT

Halocarbons such as CCl 2  F, CF 3  CFHCl 2  or CF 3  CFCl 2  which contain chlorine and/or bromine are contacted with hydrogen in the presence of silicon carbide and/or a metal selected from aluminum, molybdenum, titanium, nickel, iron or cobalt (or their alloys) at temperatures of 350° to 700° C. and pressures of 0 to 1000 psig to obtain a product wherein at least one chlorine or bromine in the starting material has been replaced by hydrogen.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a continuation of U.S. application Ser. No. 07/847,987 filed Apr. 9, 1992, now abandoned, a national filing of PCT application No. PCT/U.S. 90/05637 filed Oct. 9, 1990 claiming priority (continuation in part) of U.S. patent application Ser. No. 07/418,832 filed Oct. 10, 1989, now abandoned.

BACKGROUND OF THE INVENTION

This invention relates to a process for the hydrogenolysis of halocarbons.

At this time there is a desire to produce halocarbons of reduced chlorine content. Hydrogenolysis is a known method for doing this. For example, see U.K. Patent 1,578,933 which discloses a process for the hydrogenolysis of CF₃ CFHC1 to CF₃ CH₂ F using a hydrogenation catalyst, e.g., palladium supported on alumina or carbon. Hydrogenolysis of fluorochlorocarbons by passage through empty tubes made of various materials is also known, e.g., U.S. Pat. No. 2,615,926 discloses platinum tubes, U.S. Pat. No. 2,704,775 discloses nickel or stainless steel tubes and U.S. Pat. No. 3,042,727 discloses a Vycore® tube.

It is desired to provide a process for converting a halocarbon to a more hydrogenated form with high selectivity and particularly to provide such a process wherein formation of solids and plugging of reaction vessels is minimized.

SUMMARY OF THE INVENTION

We have discovered an improved hydrogenolysis process for reducing the chlorine and/or bromine content of halocarbons. The process may be used for producing saturated halocarbon products such that the yield loss to olefins, coupled by-products, hydrocarbons or fragmented products is less than 10%. The process involves contacting a halocarbon of the formula:

    C.sub.n H.sub.m F.sub.p X.sub.q

wherein

X is C1 or Br,

n is 1 to 10,

m is 0 to 20,

p is 0 to 21,

q is 1 to 22,

provided that m+p+q equals 2n+2 when the compound is acyclic and equals 2n when the compound is cyclic, and provided that when n is 1, q is at least 2, with at least 0.1 mole of hydrogen per mole of halocarbon at a temperature of 350° to 700° C., and a pressure of 0 to 1000 psig, in a reaction vessel (e.g., a tube) of aluminum, molybdenum, titanium, nickel, iron, cobalt, or their alloys, or of silicon carbide, optionally packed with aluminum, molybdenum, titanium, nickel, iron, cobalt or their alloys, or an inert material (e.g., silicon carbide) for a time sufficient to produce a product wherein at least one of X has been replaced by a hydrogen atom. Preferred alloys consist essentially of one or more metals selected from aluminum, molybdenum, titanium, nickel, iron and cobalt, optionally together with chromium and/or tungsten, an empty chrome-plated reaction vessel may also be used.

The process of the invention provides improved conversions and selectivity and has the further advantage that it does not produce olefins as the major product. Furthermore, the process minimizes the formation of solids in the reaction vessel, thus permitting long-term operation with less plugging.

DESCRIPTION OF THE INVENTION

An important aspect of the present invention conducting the hydrogenolysis of halocarbons in the presence of silicon carbide and/or at least one metal selected from aluminum, molybdenum, titanium, nickel, iron, cobalt or their alloys. The metals may be coated on the inside surface of a reaction vessel (e.g., by plating or sputtering the metals or their alloys onto the inside surface). Such coating can help to minimize corrosion of the reaction vessel well. A reaction vessel of these materials (e.g., a metal tube) optionally packed with the metal in suitable form or an inert material such as silica, silicon carbide or low surface area carbon (e.g., shot coke) may also be used. When reference is made to alloys, it is meant a nickel alloy containing from 1 to 99.9% (by weight) nickel, a cobalt alloy containing 1 to 99.9% (by weight) cobalt, an iron alloy containing 0.2 to 99.9% (by weight) iron, a molybdenum alloy containing 70 to 99.9% (by weight) molybdenum, an aluminum alloy containing 80 to 99.9% (by weight) aluminum and a titanium alloy containing 72 to 99.8% (by weight) titanium. Preferably the remainder of these alloys is selected such that the alloy consists essentially of (i) one or more metals selected from aluminum, molybdenum, titanium, nickel, iron and cobalt, and optionally (ii) chromium and/or tungsten.

Most preferred for the practice of this invention are nickel or alloys of nickel such as those containing 52% to 80% nickel, e.g., Inconel® 600 nickel alloy or Hastelloy® C276 alloy.

When used for packing, the metal, alloys or inert material may be particles or formed shapes such as, for example, perforated plates, saddles, rings (e.g., Pall® rings), wire, screen, chips, pipe, shot, gauze and wool. Although an empty reaction vessel (e.g., an empty tube) may be used, the use of this type of packing material can provide the advantage of minimizing backmixing. These types of packing material can also serve as heat transfer materials. In many embodiments, perforated plates, saddles and rings can be especially useful.

The invention is applicable to the hydrogenolysis of halocarbons. The halocarbons can contain 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, most preferably 1 to 3 carbon atoms. The halocarbons include cyclic as well as acyclic compounds and can be generically represented by the empirical formula C_(n) H_(m) F_(p) X_(q), where X is C1 and/or Br, preferably C1, and n is an integer from 1 to 10, m is an integer from 0 to 20, p is an integer from 0 to 21, and q is an integer from 1 to 22, provided that m+p+q=2n+2 when the compound is acyclic and equals 2n when the compound is cyclic. For single carbon compounds (i.e., n is 1) the invention is particularly applicable when q is at least 2.

In a preferred embodiment the halocarbons are represented by the above empirical formula where n=1 to 4, m is 0 to 8, p is 0 to 9, and q is 1 to 9. Preferably, when n is 2 or more, p is at least 1.

The above halocarbons are either commercially available or can be prepared by known methods or adaptation of known methods.

As previously indicated these starting materials when subjected to the process of the invention will result in products wherein one or more X (e.g., chlorine) has been replaced by hydrogen. Thus the products of the hydrogenolysis reactions of the C₁ halocarbons will contain one or two hydrogen atoms, preferably one, and those from C₂ compounds from one to three hydrogen atoms, preferably one to two. The C₃ halocarbons hydrogenolysis products will contain one to five hydrogen atoms with those containing one to four being preferred. In a similar manner the C₄ to C10 halocarbon products will contain one or more hydrogen atoms. The preferred process of this invention does not produce olefins as the major product. Instead, the major product of the conversion is a hydrogenolysis product wherein at least one X of the halocarbon starting material has been replaced by a hydrogen atom. This is particularly important for the hydrogenolysis of halocarbons where n is 2 to 10 (i.e., multicarbon halocarbons) where such factors as olefin production can be of concern at temperatures of 350° C. or more. For example, CF₃ CC1₂ F can be converted with high selectivity to a hydrogenolysis product consisting primarily of CF₃ CHC1F and CF₃ CH₂ F with very little olefin formulation. In a preferred embodiment of this invention using halocarbons containing fluorine and chlorine, at least 90% of the hydrogenolysis products contain the same number of fluorines as the original halocarbon. Furthermore the yield loss to olefins, coupled by-products, hydrocarbons, fragmentation products or carbon is less than 10%.

Examples of olefins are products such as CC1F=CCF₂ or CF₂ =CF₂ the former of which can be obtained from hydrogenolysis of CC1₂ FCC1F₂ and the latter from hydrogenolysis of CC1F₂ CC1F₂. An example of a coupled by-product is CF₃ CF=CFCF₃ which can be obtained by the hydrogenolysis of CC₁ F₂ CC1F₂. Examples of hydrocarbon products are CH₄, C₂ H₆ and C₃ H₈ which can be obtained by the hydrogenolysis of CC1₂ F₂, CC1₂ FCC1F₂ and CF₃ CC1FCF₃ respectively.

Examples of fragmentation products are CF₃ H and CH₂ F₂ which can be obtained by the hydrogenolysis of CF₃ CC1₂ F and its isomer.

The reaction temperature can range from 350° C. to 700° C. Preferably the reaction temperature is at least about 400° C.

The amount of hydrogen contained in the gas stream contacted with the gaseous halocarbon should be at least 0.1 mole per mole of halocarbon. Hydrogen amounts ranging from 0.2 to 5 moles per mole of halocarbon are used for some embodiments. In general, the amount of hydrogen preferably ranges from 0.2 to 60 moles per mole of halocarbon and more preferably ranges from 0.4 to 40 moles per mole of halocarbon. The hydrogen can be fed either in the pure state or diluted with an inert gas, e.g., nitrogen, helium, or argon.

The process pressure is operable over a broad range of pressures. Generally atmospheric (i.e., 0 psig) or superatmospheric pressures of up to 1000 psig are employed. Preferably the pressure is at least about 25 psig.

The extent of the replacement of halogen by hydrogen increases with reaction time. Reaction times between 0.1 minutes and 25 minutes are preferred. Most preferred are reaction times between 0.2 and 8 minutes.

An important feature of the process of the invention is that through selection of the appropriate metal and process conditions, a desired halocarbon hydrogenolysis product can be obtained as the major product with high selectivity and minimal formation of unwanted by-products. Preferably the reaction time and temperature are selected to obtain long term (>1000 hours) plug free operation and to provide as the major product of the conversion hydrogenolysis product which retains the fluorine content of the starting halocarbon while at least one X is replaced by hydrogen. In many embodiments the reaction time and temperature are controlled so that at least about 90% of halocarbon converted has the same number of fluorine atoms as the halocarbon starting material. Also, in many embodiments the combined yield losses to olefins, coupled by-products, hydrocarbons, or fragmentation products is less than 10%.

An additional desirable feature is that through a selection of an appropriate reaction vessel and packing (e.g., metals, alloys, or inert materials) and process conditions, the products of the hydrogenolysis can contain in high selectivity just one less chlorine or bromine than was present in the starting material. This is particularly useful when q is 2 or more, and it is desired to obtain a major product of the conversion, hydrogenolysis product which contains chlorine and/or bromine. For example, starting with a one-carbon compound containing two or more chlorine or bromine atoms, products containing just one less chlorine or bromine can be obtained in high selectivity.

Although substantial conversions can be achieved in a once-through system, recycle of unreacted halocarbons or intermediates can be employed in a conventional manner. The processes of this invention are considered to be characterized by relativity high activation energies when compared to catalytic hydrogenolysis over conventional Pd/C catalyst. For example, the activation energy for the hydrogenolysis of CF₃ CC1₂ F over a 0.5% Pd/C catalyst at 167° C. to 200° C. was found to be 14-17 Kcal/mole. The activation energy for the hydrogenolysis of CF₃ CHC1F over a 0.5% Pd/C catalyst at 249° C. to 288° C. was found to be 22-28 Kcal/mole. In contrast, the activation energies for the hydrogenolysis reactions of these compounds conducted in the reaction vessels of this invention, either empty or packed, were found to be considerably larger as exemplified in Table A.

                  TABLE A                                                          ______________________________________                                         Activation Energy Data                                                         High Temperature Hydrogenolysis                                                      Temp.                    Activation                                      Feed  Range       Packing      Energy                                          ______________________________________                                         F114.sub.a.sup.1                                                                     450-550° C.                                                                         --           49 ± 3 Kcal/mole                             F114.sub.x.sup.2                                                                     440-600° C.                                                                         --           47 ± 2                                       F124.sup.3                                                                           510-600° C.                                                                         --           49 ± 7                                       F114.sub.x                                                                           400-570° C.                                                                         shot coke    35 ± 1                                       F114.sub.x                                                                           400-500° C.                                                                         nickel screen                                                                               34 ± 3                                       F124  510-570° C.                                                                         Inconel ® screen                                                                        41 ± 3                                       F124  520-580° C.                                                                         shot coke    37 ± 1                                       ______________________________________                                          .sup.1 F114.sub.a = CF.sub.3 CCl.sub.2 F                                       .sup.2 F114.sub.x = Du Pont commercial CClF.sub.2 CClF.sub.2 containing        some CF.sub.3 CCl.sub.2 F                                                      .sup.3 F124 = CF.sub.3 CHClF                                             

The products of the reaction can be separated and purified by conventional means. The products can be used as solvents, blowing agents, refrigerants and propellants.

Practice of the invention will become further apparent from the following non-limiting examples. In the following Examples the following general procedure was employed, unless otherwise indicated.

General Procedure--A flow reactor under microprocessor control was used. The reactor, unless otherwise indicated, was a 15"×1/4" o.d. or 3/8" o.d. Inconel® 600 nickel alloy tube or a 15"×3/8" Hastelloy® C276 nickel alloy tube bent into a U shape and immersed in a heated fluidized sand bath for temperature control. Inconel® 600 is a commercial alloy containing 76% nickel, 15.5% chromium and 8% iron. Hastelloy® C-276 is a commercial alloy containing 59% nickel, 15.5% chromium, 16% molybdenum and 3.75% tungsten.

The reactor was used either empty or filled with various packing materials as described in the Examples. Hydrogen gas was metered into the system through mass flow controllers. Liquid halocarbons were fed from a syringe pump and vaporized before entering the reactor. Conversions and yields were measured by taking gas stream samples into a gas chromatograph. Product identification was by gc retention times with confirmation by gc-mass spectrometer analysis of samples.

EXAMPLE 1 CF₃ CC1₂ F+H₂ →CF₃ CHC1F+CF₃ CH₂ F

2,2-Dichloro-1,1,1,2-tetrafluoroethane (1.47 g/hr) and hydrogen (molar ratio of H₂ /CF₃ CC1₂ F =1.9) were fed into the 1/4" empty Inconel® nickel alloy reactor for 38 hours at 450°-550° C. and 250 psig. A sample taken after 14 hours at 550° C. showed an 89% conversion of CF₃ CC1₂ F with a 65% selectivity to CF₃ CHC1F and a 32% selectivity to CF₃ CH₂ F. Overall selectivity to the two products was 97%.

EXAMPLE 2 CF₃ CC1₂ F+H₂ →CF₃ CHC1F+CF₃ CH₂ F

2,2-Dichloro-1,1,1,2-tetrafluoroethane (1.47 g/hr) and hydrogen (molar ratio of H₂ /CF₃ CC1₂ F =1.9) were fed into the 1/4" empty Inconel® nickel alloy reactor for 132 hours at 350°-550° C. and 250 psig. At 350° C. a 2.3% conversion of CF₃ CC1₂ F with a 76% selectivity to CF₃ CHC1F and CF₃ CH₂ F was observed. A sample taken after 20 hours at 500° C. showed an 83% conversion of CF₃ CC1₂ F with a 98% selectivity to CF₃ CHC1F and CF₃ CH₂ F.

EXAMPLE 3 CF₃ CHC1F+H₂ →CF₃ CH₂ F

2-Chloro-1,1,1,2-tetrafluoroethane (1.0 g/hr) and hydrogen (molar ratio of H₂ /CF₃ CC1₂ F=4.9) were fed into the 1/4" empty Inconel® nickel alloy reactor for 7 hours at 550° C. and 250 psig with average CF₃ CHC1F conversions of 86% with 98% selectivity to CF₃ CH₂ F and 0.4% selectivity to CF₃ CH₃.

EXAMPLE 4 CF₂ C1₂ +H₂ →CF₂ HC1

Dichlorodifluoromethane (9.0 g/hr) and hydrogen (molar ratio of H₂ /CF₂ C1₂ =1.0) were fed into the 1/4" empty Inconel® nickel alloy reactor as described above for 89 hours at 300 psig, including 79 hours at 500°-550° C. For 12 hours at 500° C. during this run, at a mean age of 64 synthesis hours, the average conversion of CF₂ C1₂ was 26% with a 97% selectivity to CF₂ HC1 and a 3% selectivity to CH₂ F₂.

EXAMPLE 5 CF₃ CC1FCF₃ +H₂ →CF₃ CHFCF₃

2-Chloroheptafluoropropane (1.5 g/hr) and hydrogen (22 cc/min) were fed into the 1/4" empty Inconel® nickel alloy reactor for 3 hours at 450° C. and 250 psig with 30-40% conversion and a 98% selectivity to CF₃ CHFCF₃.

EXAMPLE 6 CF₃ CC1FCF₃ +H₂ →CF₃ CHFCF₃

2-Chloroheptafluoropropane (1.38 g/hr) and hydrogen (22 cc/min) were fed into the 1/4" Inconel® nickel alloy reactor filled with Inconel® nickel alloy chips (10 g). Operation at 500° C. and 250 psig for 33.3 hours gave an average of 91.3% conversion with 99.4% selectivity to CF₃ CHFCF₃.

EXAMPLE 7 CF₃ CC1₂ F+H₂ →CF₃ CHC1F+CF₃ CH₂ F

2,2-Dichloro-1,1,1,2-tetrafluoroethane (2.9 or 5.9 g/hr) and hydrogen (molar ratio of H₂ /CF₃ CC1₂ F=2.2 or 4.3) were fed into the 3/8" Inconel® nickel alloy reactor filled with Inconel® nickel alloy wool (7.96 g) for 106 hours at 400°-500° C. and 250 psig. The average conversion of CF₃ CC1₂ F over the whole period was 99.9%. For a 12-hour period at 450° C. with a CF₃ CC1₂ F feed rate of 5.9 g/hr (molar ratio H₂ /CF₃ CC1₂ F=4.3) the following average selectivities were observed: 69% CF₃ CHC1F and 26% CF₃ CH₂ F.

EXAMPLE 8 CF₃ CHC1F+H₂ →CF₃ CH₂ F

2-Chloro-1,1,1,2-tetrafluoroethane (5.5 g/hr) and hydrogen (molar ratio of H₂ /CF₃ CHC1F=1.1) were fed into the 3/8" Inconel® nickel alloy reactor filled with a pure nickel screen (8.77 g), operated at various feed rates and a pressure of 300 psig. With a CF₃ CHC1F feed rate of 5.48 g/hr and hydrogen (molar ratio of H₂ /CF₃ CHC1F=1.1) conversion at 525° C. and an average synthesis time of 82 hours averaged 47% with 98% selectivity to CF₃ CH₂ F for 12 hours. At an average synthesis time of 644 hours conversion averaged 39% with 97% selectivity to CF₃ CH₂ F. At 1181 synthesis hours the operating pressure was increased to 500 psig. Conversion of CF₃ CHC1F averaged 68% for 14 hours with a selectivity to CF₃ CH₂ F of 98%.

EXAMPLE 9 CF₃ CHC1F+H₂ →CF₃ CH₂ F

2-Chloro-1,1,1,2-tetrafluoroethane (2.7 or 5.5 g/hr) and hydrogen (molar ratio of H₂ /CF₃ CHC1F=1.9) were fed into the 3/8" Inconel® nickel alloy reactor filled with Inconel® nickel alloy wool (7.96 g) for 23 hours at 400°-500° C. and 250 psig. Between 18 and 23 hours, at 400° C. with a CF₃ CHC1F feed rate of 2.7 g/hr, the average conversion was 23% and the selectivity to CF₃ CH₂ F was 82%.

EXAMPLE 10 CF₂ C1₂ +H₂ →CF₂ HC1

Dichlorodifluoromethane (4.5 or 33.0 g/hr) and hydrogen (molar ratio of H₂ /CF₂ C1₂ =1 or 0.5) were fed into the 3/8" Inconel® nickel alloy reactor filled with pure nickel screen (17.5 g) for 135 hours at 300 psig. For 12 hours at 450° during this run, at a mean synthesis time of 78 hours, with a CF₂ C1₂ feed rate of 4.5 g/hr (molar ratio H₂ /CF₂ C1₂ =1.0), the average conversion of CF₂ C1₂ was 34% with the following average selectivities: 95% CF₂ HC1 and 2.9% CF₂ H₂.

EXAMPLE 11 CF₃ CC1F₂ +H₂ →CF₃ CHF₂

Chloropentafluoroethane vapor (6 cc/min) and hydrogen (5 cc/min) were fed into a Hastelloy® nickel alloy reactor (6"×1/2" O.D.) filled with pure nickel screen (39.68 g) at 550° C. and atmospheric pressure. The reaction products were analyzed with the following results: 59% conversion of CF₃ CC1F₂ with a 97% selectivity to CF₃ CHF₂.

EXAMPLE 12 CF₃ CC1F₂ +H₂ →CF₃ CHF₂

Chloropentafluoroethane vapor (5 cc/min) and hydrogen (6 cc/min) were fed into an Inconel® nickel alloy reactor (6"×1/2" O.D.) filled with pure nickel screen (51-98 g) at 550° C. and atmospheric pressure. The reaction products were analyzed with the following results: 65% conversion of CF₃ CC1F₂ with a 95% selectivity to CF₃ CHF₂.

The reaction was run under the same conditions as described above, except that the feed rates were changed to CF₃ CC1F₂ (5 cc/min) and H₂ (12 cc/min). The reaction products were analyzed with the following results: 62% conversion of CF₃ CC1F₂ with an 86% selectivity to CF₃ CHF₂.

EXAMPLE 13 CC1F₂ CC1F₂ /CF₃ CC1₂ F+H₂ →CHF₂ CC1F₂ /CF₃ CHC1F+CHF₂ CHF₂ /CF₃ CH₂ F

A vapor mixture of CC1F₂ CC1F₂ (9)/CF₃ CC1₂ F(1) (5 cc/min) and hydrogen (6 cc/min) was fed into a Hastelloy® nickel alloy reactor (6"×1/2" O.D.) filled with pure nickel screen (39.68 g) at 550° C. and atmospheric pressure. The reaction products were analyzed with the following results: 61% conversion of CC1F₂ CC1F₂ /CF₃ CC1₂ F with a 46% selectivity to CHF₂ CC1F₂ /CF₃ CHC1F and a 34% selectivity to CHF₂ CHF₂ /CF₃ CH₂ F.

EXAMPLE 14 CF₃ CC1₂ F+H₂ →CF₃ CHC1F+CF₃ CH₂ F

2,2-Dichlorotetrafluoroethane vapor (5 cc/min) and hydrogen (6 cc/min) were fed into an Inconel® nickel alloy reactor (6"×1/2" O.D.) filled with pure nickel screen (51.98 g) at 550° C. and atmospheric pressure. The reaction products were analyzed with the following results: 83% conversion of CF₃ CC1₂ F with a 5% selectivity to CF₃ CHC1F and a 66% selectivity to CF₃ CH₂ F.

EXAMPLE 15 CF₃ CHC1F+H₂ →CF₃ CH₂ F

2-Chloro-1,1,1,2-tetrafluoroethane vapor (5 cc/min) and hydrogen (6 cc/min) were fed into an Inconel® nickel alloy reactor (6"×1/2" O.D.) filled with pure nickel screen (51.98 g) at 550° C. and atmospheric pressure. The reaction products were analyzed with the following results: 58% conversion of CF₃ CHC1F with an 85% selectivity to CF₃ CH₂ ^(F).

EXAMPLE 16 CC1F₂ CC1₂ F+H₂ →CHC1FCC1F₂ +CHC1FCHF₂

1,1,2-Trichloro-1,2,2-trifluoroethane (3.13 g/hr) and hydrogen (molar ratio=4.75) were fed into the 3/8" Inconel® nickel alloy U-tube reactor as described in the general procedure, with the exit leg filled with pure nickel screen (8 g), at 450° C. and 500 psig. Over a 6-hour period the reaction products were analyzed with the following results: 81% conversion of CC1₂ FCC1F₂ with 96% combined selectivity to C₂ H₃ F₃, C₂ H₂ C1F₃, and C₂ HC1₂ F₃. Selectivity to CC1F=CF₂ was 2%. When the temperature was raised to 475° C. for 7 hours, the average conversion of CC1₂ FCC1F₂ was 97% with 95% combined selectivity to C₂ H₃ F₃, C₂ H₂ C1F₃, and C₂ HC1₂ F₃. Selectivity to CC1 F=CF₂ was 1%.

EXAMPLE 17 CF₃ CHC1F+H₂ →CF₃ CH₂ F

2-Chloro-1,1,1,2-tetrafluoroethane (2.7 g/hr) and hydrogen (molar ratio of H₂ /CF₃ CHC1F=0.2) were fed into an empty 6"×1/2" O.D. Hastelloy® C276 nickel alloy reactor for 8 hours at 535° C. and 300 psig. The average conversion of CF₃ CHC1F was 22% with an average 97% CF₃ CH₂ F selectivity.

EXAMPLE 18 CF₃ CHC1F+H₂ →CF₃ CH₂ F

2-Chloro-1,1,1,2-tetrafluoroethane (2.7 g/hr) and hydrogen (molar ratio of H₂ /CF₃ CHC1F=1.5) were fed into 6"×1/2 O.D. Hastelloy® C276 nickel alloy reactor containing 14/20 mesh acid-washed SiC (6.5 g) for 60 hours at 535° C. and 300 psig. The average conversion of CF₃ CHC1F was 75% with an average 97% CF₃ CH₂ F selectivity.

EXAMPLE 19 CF₃ CHC1F+H₂ →CF₃ CH₂ F

2-Chloro-1,1,1,2-tetrafluoroethane and hydrogen were fed at various rates over 113 hours into the 3/8" Hastelloy® C276 nickel alloy tube operated at 300 psig and containing Conoco Shot coke (9.2 grams, 10 cc), a highly fused petroleum coke with a surface area of 0.5 sq m/g. For an 8-hour period at 560° C. and an average time in synthesis of 102 hours, with a CF₃ CHC1F feed rate of 11.0 g/hr and a hydrogen feed rate of 32 cc/min (molar ratio of H₂ /CF₃ CHC1F=1) the average conversion of CF₃ CHC1F was 13% with an average selectivity to CF₃ CH₂ F of 99%.

EXAMPLE 20 CC1F₂ CC1F₂ +H₂ →CHF₂ CC1F₂ +CHF₂ CHF₂

Commercial 1,2-dichloro-1,1,2,2-tetrafluoroethane, containing 9% (molar) 1,1-dichloro-1,2,2,2-tetrafluoroethane, and hydrogen were fed at various rates over 150 hours into the 3/8" Inconel® nickel alloy tube operated at 300 psig and containing Conoco Shot coke (9.2 grams, 10 cc), a highly fused petroleum coke with a surface area of 0.5 sq. m/g. For a 16-hour period at 550° C. and an average time in synthesis of 59 hours, with a CC1F₂ CC1F₂ feed rate of 5.9 g/hr and a hydrogen feed rate of 28 cc/min (molar ratio of H₂ /CC1F₂ CC1F₂ =2) the average conversion of the C₂ C1₂ F₄ isomers was 84% with an average selectivity to CHF₂ CC1F₂ and its isomer of 49%, and an average selectivity to CHF₂ CHF₂ and its isomer of 47%.

EXAMPLE 21 CF₃ CC1₂ F+H₂ →CF₃ CHC1F+CF₃ CH.sub. 2 F

2,2-Dichloro-1,1,1,2-tetrafluoroethane (2 mL/h), which was vaporized before being mixed with hydrogen (13 cc/min), was fed into a Hastelloy® C nickel alloy reactor (6"×1/2 O.D.) as described above, containing Conoco Shot coke (14.0 grams, 10 mesh), a highly fused petroleum coke with a surface area of 0.5 sq m/g at 550° C. and 100 psig. After 28 hours of operation, product analysis indicated that CF₃ CC1₂ F conversion was quantitative and selectivity to CF₃ CHC1F and CF₃ CH₂ F was 64.7% and 33.3% respectively.

EXAMPLE 22 CF₃ CC1F₂ +H₂ →CF₃ CHF₂

Chloropentafluoroethane vapor (10 cc/min) and hydrogen (10 cc/min) were fed into a Hastalloy® C nickel alloy reactor (6"×1/2" O.D.) as described above, charged with Conoco Shot coke (14.0 grams, 10 mesh), a highly fused petroleum coke with a surface area of 0.5 sq m/g at 550° C. After 10 hours of operation, product analysis indicated that CF₃ CC1F₂ conversion was 7.5% and selectivity to CF₃ CHF₂ was 94.7%.

This experiment was substantially repeated except that the CF₃ CC1F₂ flow was 5 cc/min and the hydrogen flow was 6 cc/min. Product analysis indicated that CF₃ CC1F₂ conversion was 13.3% and selectivity to CF₃ CHF₂ was 89.6%.

EXAMPLE 23 CC1F₂ CC1F₂ +H₂ →CHF₂ CC1F₂ +CHF₂ CHF₂

Commercial 1,2-dichloro-1,1,2,2-tetrafluoroethane, containing 9% (molar) 1,1-dichloro-1,2,2,2-tetrafluoroethane, and hydrogen were fed at various rates for 172 hours into an empty 15"×3/8" O.D. Hastelloy® C276 nickel alloy tube, as described above, operated at 500 psig. For a 13 hour period at 500° C. and an average time in synthesis of 66 hours, with a CC1F₂ CC1F₂ feed rate of 5.9 g/hr and hydrogen feed rate of 10 cc/min (molar ratio of H₂ /CC1F₂ CC1F₂ =0.7) the average conversion of C.sub. C1₂ F₄ isomers was 58% with an average selectivity to CHF₂ CC1F₂ and its isomer of 75% and an average selectivity to CHF₂ CHF₂ and its isomer of 24%. For a 9 hour period at 500° C. and an average time in synthesis of 148 hours, with a CC1F₂ CC1F₂ feed rate of 1.47 g/hr and a molar feed ratio of H₂ /CC1F₂ CC1F₂ of 1.5 the average conversion of C₂ C1₂ F₄ isomers was 88% with an average selectivity of CHF₂ CC1F₂ and its isomer of 45% and an average selectivity to CHF₂ CHF₂ and its isomer of 54%.

EXAMPLE 24 CC1F₂ CC1F₂ +H₂ →CHF₂ CC1F₂ +CHF₂ CHF₂

Commercial 1,2-dichloro-1,1,2,2-tetrafluoroethane, containing 9% (molar) 1,1-dichloro-1,2,2,2-tetrafluoroethane, and hydrogen were fed at various rates for 192 hours into a 15"×3/8" O.D. Inconel® 600 nickel alloy tube, as described above, containing 8.0 g of 24×100 mesh nickel screen and operated at 500 psig. For a 10 hour period at 400° C. and a CC1F₂ CC1F₂ feed rate of 0.7 g/hr and hydrogen feed rate of 1.7 cc/min (molar ratio of H₂ /CC1F₂ CC1F₂ =1); the average conversion of C.sub. C1₂ F₄ isomers was 61% with an average selectivity to CHF₂ CC1F₂ and its isomer of 77.0% and an average selectivity to CHF₂ CHF₂ and its isomer of 22.7%.

EXAMPLE 25 CF₃ CC1₂ F+H₂ →CF₃ CHC1F+CF₃ CH₂ F

2,2-Dichloro-1,1,1,2-tetrafluoroethane and hydrogen were fed at various rates for 68 hours to an empty Hastelloy® C276 nickel alloy tube, as described above, operated at 500 psig. For a five hour period at 500° C. and an average time in synthesis of 41 hours, with a CF₃ CC1₂ F feed rate of 5.9 g/hr and a hydrogen rate of 14 cc/min (molar ratio of H₂ /CF₃ CC1₂ F=1), the average conversion was 64% with an average selectivity to CF₃ CHC1F of 83.6 and an average selectivity of CF₃ CH₂ F of 15.6%.

EXAMPLE 26 CC1F₂ CC1F₂ +H₂ →CHF₂ CC1F₂ +CHF₂ CHF₂ Chrome-Plated Reactor

Commercial 1,2-dichloro-1,1,2,2 tetrafluoroethane, containing 9% (molar) 1,1-dichloro-1,2,2,2-tetrafluoroethane, and hydrogen were fed at various rates over 55 hours into a 15"×1/4" o.d. empty chrome-plated U-tube reactor, as described above, operated at 300 psig. For a 20-hour period at 500° C. and an average time in synthesis of 16 hours, with a CC1F₂ CC1F₂ feed rate of 2.9 g/hr and a hydrogen feed rate of 13.3 cc/min (molar ratio H₂ /CC1F₂ CC1F₂ =2); the average conversion of the CC1F₂ CC1F₂ isomers was 56% with an average selectivity to CHF₂ CC1F₂ and its isomer of 21%, and an average selectivity to CHF₂ CHF₂ and its isomer of 76%.

EXAMPLE 27 CC1F₂ CC1F₂ +H₂ →CHF₂ CC1F₂ +CHF₂ CHF₂ Aluminum Reactor

Commercial 1,2-dichloro-1,1,2,2 tetrafluoroethane, containing 9% (molar) 1,1-dichloro-1,2,2,2 tetrafluoroethane, and hydrogen were fed at various rates over 31 hours into an empty 15"×1/4" o.d. aluminum U-tube reactor, as described above, operated at 50 psig. For a 3-hour period at 500° C. and an average time in synthesis of 28 hours, with a CC1F₂ CC1F₂ feed rate of 1.47 g/hr and a hydrogen feed rate of 7.0 cc/min (molar ratio H₂ /CC1F₂ CC1F₂ =2); the average conversion of the CC1F₂ CC1F₂ isomers was 5% with an average selectivity to CHF₂ CC1F₂ and its isomer of 49%, and an average selectivity to CHF₂ CHF₂ and its isomers of 33%.

EXAMPLE 28 CC1F₂ CC1F₂ +H₂ →CHF₂ CC1F₂ +CHF.sub. 2 CHF₂ Titanium Reactor

Commercial 1,2-dichloro-1,1,2,2-tetrafluoroethane, containing 9% (molar) 1,1-dichloro-1,2,2,2-tetrafluoroethane, and hydrogen were fed at various rates over 42 hours into a 15"×1/4" o.d. empty titanium U-tube reactor, as described above, operated at 50 psig. For a 17-hour period at 500° C. and an average time in synthesis of 9.5 hours, with a CC1F₂ CC1F₂ feed rate of 2.9 g/hr and a hydrogen feed rate of 13.9 cc/min (molar ratio H₂ /CC1F₂ CC1F₂ =2) the average conversion of the CC1F₂ CC1F₂ isomers was 14.2% with an average selectivity to CHF₂ CC1F₂ and its isomer of 57%, and an average selectivity to CHF₂ CHF₂ and its isomer of 24.4%.

EXAMPLE 29

CF₃ CHC1F+H₂ →CF₃ CH₂ F

Silicon Carbide Reactor

2-Chloro-1,1,1,2-tetrafluoroethane and hydrogen were fed at various rates over 47 hours into a 15"×1/4" o.d. empty silicon carbide straight tube reactor, as described above, operated at 0 psig. For a 12-hour period at 600° C. and an average time in synthesis of 29 hours, with a CF₃ CHC1F feed rate of 2.74 g/hr and a hydrogen feed rate of 8.2 cc/min (molar ratio H₂ /CF₃ CHC1F=1); the average conversion of the CF₃ CHC1F was 4.3%, with an average selectivity to CF₃ CH₂ F of 89.7%.

EXAMPLE 30 CF₃ CC1₂ F+H₂ →CF₃ CHC1F+CF₃ CH₂ F Silicon Carbide Reactor

2,2-Dichloro-1,1,1,2-tetrafluoroethane 2.94 g/hr were fed into a silicon carbide straight tube reactor, as described above, with 6.4 cc/min of hydrogen (molar ratio H₂ /CF₃ CC1₂ ^(F) =1) operated at 0 psig for 41 hours. Over a 15-hour period at 500° C. and an average time in synthesis of 27 hours; the average conversion of CF₃ CC1₂ F was 23% with an average selectivity to CF₃ CHC1F of 54% and an average selectivity to CF₃ CH₂ F of 0.6%.

EXAMPLE 31 CC1F₂ CC1F₂ +H₂ →CHF₂ CC1F₂ +CHF₂ CHF₂ Silicon Carbide Reactor

Commercial 1,2-dichloro-1,1,2,2 tetrafluoroethane, containing 9% (molar) 1,1-dichloro-1,2,2,2 tetrafluoroethane, and hydrogen were fed at various feed rates over 38 hours into a straight tube silicon carbide reactor tube, as described above, operated at 0 psig. For a 12-hour period at 575° C. and at an average time in synthesis of 14 hours, with a feed rate of 13.9 cc/min of hydrogen and 2 grams/hr of CC1F₂ CC1F₂ (molar ratio H₂ /CC1F₂ CC1F₂ =2); the average conversion of the CC1F₂ CC1F₂ isomers was 35.6% with an average selectivity to CHF₂ CC1F₂ and its isomers of 28% and an average selectivity to CHF₂ CHF₂ and its isomers of 27%.

EXAMPLE 32 CF₂ C1₂ +H₂ →CF₂ HC1+CH₂ F₂ Silicon Carbide Reactor

Dichlorodifluoromethane (2.6 g/hr) and hydrogen (molar ratio H₂ /CF₂ C1₂ =1.0) were fed into an empty 1/2"×15" silicon carbide straight tube reactor, as described above, over a 2S-hour period. For four hours at 575° C. during this run, at an average synthesis time of 26 hours;-the average conversion of CF₂ C1₂ was 35.6% with an 82% selectivity to CF₂ HC1 and a 2% selectivity to CH₂ F₂.

EXAMPLE 33 CF₃ CC1₃ +H₂ →CF₃ CHC1₂ +CF₃ CH₂ C1 Hastelloy® Nickel Alloy Reactor

1,1,1-Trichloro-2,2,2-trifluoroethane and hydrogen were fed into an empty 15"×3/8" Hastelloy® C276 nickel alloy U-tube reactor, as described above, at 300 psig for a period of 28 hours. Over a 6-hour period at 425° C. and 300 psig, at an average time in synthesis of 17 hours, with a feed rate of CF₃ CC1₃ of 6.25 g/hr and a hydrogen feed rate of 14.0 sccm (molar ratio H₂ /CF₃ CC1₃ =1.0); the average conversion of CF₃ CC1₃ was 33% with a selectivity to CF₃ CHC1₂ of 95% and a selectivity to CF₃ CH₂ C1 of 5%.

EXAMPLE 34 CC14+H₂ →CHC1₃ +CH₂ C1₂ Inconel® Nickel Alloy Reactor

Carbon tetrachloride (6.57 g/hr) and hydrogen (200 sccm) were fed into an empty 15"×1/4" Inconel® 600 nickel alloy U-tube reactor, as described above, operated at pressures between 0 psig and 300 psig for 149 hours. For a 10-hour period at 457° C. and 300 psig and an average time in synthesis of 136 hours, with a CC1₄ feed rate of 6.57 g/hr and a hydrogen feed rate of 200 sccm (molar ratio H₂ /CC1₄ =12); the average conversion of CC1₄ was 45% with an average selectivity to CHC1₃ of 59% and an average selectivity to CH₂ C1₂ of 2.8%.

EXAMPLE 35 CF₃ CHC1F+H₂ →CF₃ CH₂ F High Hydrogen Ratio

2-Chloro-1,1,1,2-tetrafluoroethane and hydrogen were fed at varying rates for over 48 hours to a 56" ×1/4" Inconel® 600 nickel alloy coil reactor at 300 psig and temperatures between 550 and 600° C. For 4 hours at 600° C., at an average time in synthesis of 39 hours, with a CF₃ CHC1F feed rate of 1.6 mL/hr and a H₂ feed rate of 130 sccm (H₂ /CF₃ CHC1F mol ratio=20) the average conversion of CF₃ CHC1F was 83% and the selectivity to CF₃ CH₂ F was 944. At a lower H₂ flow of 65 sccm and the same CF₃ CHC1F feed rate and temperature (H₂ /CF₃ CHC1F mol ratio=10) the average conversion of CF₃ CHC1F over a 5-hour period was 90% with a 94% selectivity to CF₃ CH₂ F.

EXAMPLE 36 CF₃ CHC1F+H₂ →CF₃ CH.sub. 2 F High Hydrogen Ratio

2-Chloro-1,1,1,2-tetrafluoroethane and hydrogen were fed at various rates for 1207 hours into a 15"×3/8" Inconel® 600 nickel alloy U-tube, packed with 8.77 g 150 mesh nickel screen, and operated at various temperatures at 300 psig. For a 23-hour period at 550° C. and an average time in synthesis of 755 hours with a CF₃ CHC1F feed rate of 0.4 ml/hour and a hydrogen feed rate of 18 sccm/min (molar ratio H₂ /CF₃ CHC1F=11), the average conversion of CF₃ CHC1 was 99.64 with a selectivity to CF₃ CH₂ F of 93%.

EXAMPLE 37 CC1₂ FCF₃ +H₂ →CHC1FCF₃ +CH₂ FCF₃ High Hydrogen Ratio

1,1-Dichloro-1,2,2,2-tetrafluoroethane and hydrogen were fed at various rates for 237 hours into a 15"×3/8" Hastelloy® C nickel alloy U-tube packed with 9.29 g of Conoco shot coke and operated at various temperatures at 300 psig. For a 5-hour period at 575° C. and an average time in synthesis of 227 hours with a CC1₂ FCF₃ feed rate of 36 mL/hr and a hydrogen feed rate of 50 sccm/min (molar ratio H₂ /CC1₂ FCF₃ =40), the average conversion of CC1₂ FCF₃ was 100%. The selectivity to CHC1FCF₃ was 32% and the selectivity to CH₂ FCF₃ was 59%.

EXAMPLE 38 CF₃ CC1F₂ +H₂ →CF₃ CHF₂

2-Chloro-1,1,1,2,2-pentafluoroethane and hydrogen were fed at various rates to 15"×3/8" Hastelloy® C276 nickel alloy U-tube operated at 300 psig and various temperatures for 136 hours. For 10 hours, at an average time in synthesis of 58 hours and a temperature of 575° C., with a CF₃ CC1F₂ feed rate of 2.1 g/hr and a hydrogen feed rate of 14.0 sccm (molar ratio H₂ /CF₃ CC1F₂ =2.5), the conversion of CF₃ CC1F₂ was 89.5% and the selectivity to CF₃ CHF₂ was 99.9%.

For an 8-hour period at an average time in synthesis of 131 hours and a temperature of 575° C., with a feed rate of CF₃ CC1F₂ of 4.15 g/hr and a hydrogen feed rate of 329 sccm (molar ratio H₂ /CF₃ CC1F₂ =30), the average conversion of CF₃ CC1F₂ was 39% with a selectivity to CF₃ CHF₂ was 99.6%.

Particular embodiments of the invention are included in the examples. Other embodiments will become apparent to those skilled in the art from a consideration of the specification or practice of the invention disclosed herein. It is understood that modifications and variations may be practiced without departing from the spirit and scope of the novel concepts of this invention. It is further understood that the invention is not confined to the particular formulations and examples herein illustrated, but it embraces such modified forms thereof as come within the scope of the following claims. 

We claim:
 1. A process for the hydrogenolysis of a halocarbon starting compound selected from the group consisting of CF₃ CC1₂ F, CF₃ CHC1F, CF₃ CC1FCF₃, CC1F₂ CC1F₂, CF₃ CC1₃ and CF₃ CC1F₂ comprising contracting said halocarbon starting compound with at least 0.1 mole of hydrogen per mole of said halocarbon starting compound in an empty reaction vessel of nickel, iron or their alloys at a pressure within the range of from 0 psig to 1000 psig, at a temperature within the range of from 350° C. to 700° C. and for a time sufficient to produce a hydrogenolysis product wherein at least one chlorine has been replaced by hydrogen, at least 90% of the product of said hydrogenolysis containing the same number of fluorines as said halocarbon starting compound.
 2. The process of claim 1 wherein the halocarbon starting compound is selected from CF₃ CC1₂ F, CF₃ CHC1F and CC1F₂ CC1F₂.
 3. The process of claim 1 wherein the reaction vessel is nickel or a nickel alloy.
 4. The process of claim 1 wherein the temperature ranges from 400° C. to 700° C.
 5. The process of claim 4 wherein the pressure is 0 to 500 psig.
 6. The process of claim 5 wherein the halocarbon starting compound is CC1F₂ CC1F₂, the reaction vessel is nickel or a nickel alloy, and the reaction time is between 0.2 to 8 minutes.
 7. The process of claim 5 wherein the halocarbon starting compound is CF₃ CC1₂ F, the reaction vessel is nickel or a nickel alloy, and the reaction time is between 0.2 and 8 minutes.
 8. The process of claim 5 wherein the halocarbon starting compound is CF₃ CHC1F, the reaction vessel is nickel or a nickel alloy, and the reaction time is between 0.2 and 8 minutes.
 9. The process of claim 5 wherein the halocarbon starting compound is CF₃ CC1F₂, the reaction vessel is nickel or a nickel alloy, and the reaction time is between 0.2 and 8 minutes.
 10. The process of claim 5 wherein the halocarbon starting compound is CF₃ CC1₃, the reaction vessel is nickel or a nickel alloy, and the reaction time is between 0.2 and 8 minutes.
 11. The process of claim 5 wherein the halocarbon starting compound is CF₃ CC1FCF₃, the reaction vessel is nickel or a nickel alloy, and the reaction time is between 0.2 and 8 minutes.
 12. The process of claim 1 wherein the reaction vessel is either an alloy containing about 76 percent nickel, about 15.5 percent chromium and about 8 percent iron or an alloy containing about 59 percent nickel, about 15.5 percent chromium, about 16 percent molybdenum and about 3.75 percent tungsten.
 13. The process of claim 1 wherein a halocarbon starting compound selected from CF₃ CC1₂ F, CF₃ CHC1F, CC1F₂ CC1F₂, CF₃ CC1₃ and CF₃ CC1F₂, is contacted with at least about 2 moles of hydrogen per mole of said starting compound in a nickel alloy reaction vessel.
 14. The process of claim 1 wherein the halocarbon starting compound is selected from CF₃ CC1₂ F, CC1F₂ CC1F₂ and CF₃ CC1₃ and wherein the hydrogenolysis is conducted at a temperature within the range of from 350° C. to 700° C. for a time sufficient to produce as the major product of the hydrogenolysis, hydrogenolysis product wherein just one chlorine has been replaced by hydrogen.
 15. A process for the hydrogenolysis of a halocarbon starting compound selected from the group consisting of CF₃ CC1₂ F, CF₃ CHC1F, CF₃ CC1FCF₃, CC1F₂ CC1F₂, CF₃ CC1₃ and CF₃ CC1F₂ comprising contacting said starting compound with at least 0.1 mole of hydrogen per mole of said halocarbon starting compound in an empty chrome plated reaction vessel at a pressure within the range of from 0 psig to 1000 psig, at a temperature within the range of from 350° C. to 700° C. and for a time sufficient to produce a hydrogenolysis product wherein at least one chlorine has been replaced by hydrogen, at least 90% of the product of said hydrogenolysis containing the same number of fluorines as said halocarbon starting compound.
 16. The process of claim 15 wherein the temperature ranges from 400° C. to 700° C.
 17. The process of claim 16 wherein the pressure is 0 to 500 psig.
 18. A process for the hydrogenolysis of CC1F₂ CC1F₂, comprising contacting said CC1F₂ CC1F₂ with at least 0.1 mole of hydrogen per mole of said CC1F₂ CC1F₂ in an empty chrome-plated reaction vessel at a pressure within the range of from 0 psig to 1000 psig, at a temperature within the range of from 400° C. to 700° C. and for a reaction time between 0.2 to 8 minutes sufficient to produce a hydrogenolysis product wherein at least one chlorine has been replaced by hydrogen at least 90% of the product of said hydrogenolysis containing the same number of fluorines as said CC1F₂ CC1F₂. 